Polycarboxy esters of dimerized 9, 11-linolo-diricinolein and method of making same



Patented Sept. 28, 1948 POLYCARBOXY ESTERS OF DHHEBIZED 9,11-

LINOLO-DIRICINOLEIN AND METHOD OF MAKING SAME Melvin De Groote,University City, MO., assignor to Petrolite Corporation, Ltd.,Wilmington, DeL, a corporation Delaware No Drawing. Original applicationJuly 13, 1945,

Divided and this application November 5, 1946, Serial No. 707,977

8 Claims. (01. 260-405) Serial No. 604,990.

This invention relates to certain new chemical products or compounds andto the manufacture of same, my present application being a division ofmy co-pending application Serial No. 604,990, filed July 13, 1945, nowU. S. Patent 2,417,738, issued March 18, 1947.

One object of my invention is to provide new chemical products orcompounds that are particularly. adapted for use as a demulsifler in theresolution of crude oil-emulsions, but which are also adapted forvarious other uses, as hereinafter described.

Anot-her'obiect of my invention is to provide a practical method ofmaking the said chemical products or compounds.

The new chemical product herein described, particularly when employed asa demulsiiier, consists of a partial or fractional ester derived byreaction between a polycarboxy acid or anhydride, such as phthalic acid,and the dimer of what may be most conveniently referred to as9,1l-linolo-diricinolein. The conventional dehydration of castor oil orricinoleic acid, or'some other ester, results in the formation of adiene acid with the probability that two reactions ordinarily go toapproximately the same degree. These reactions may be illustrated in thefollowing manner:

Reaction 1 (9, l l-linolcic acid) March 26, 194-0, Priester; 2,209,065,dated July 23,

2 1940, Pelikan; 2,212,385, dated August 20, 1940, Brod; 2,226,830,dated December 31. 1940. Priester; 2,226,831, dated December 31, 1940,Priester; 2,246,768, dated June 24, 1941. Ubben: 2,261,663, datedNovember 3, 1941 Rheineck;

2,336,186, dated December 7, 1943, Nessler:

2,351,444, dated June 13, 1944, Miller.

The mixed isomers may be treated so as to convert the unconJugatedisomer into the coniugated isomer. This isomerization reaction may beindicated thus:

(9,11-linoleic acid) U. 8. Patents exemplifying isomerization procedureof the kind indicated, are the following: No. 2,185,414, dated January2, 1940, McKinney; 2,242,230, dated May 20, 1941, Burr; 2,350,583, datedJune 6, 1944, Bradley.

9,11-linoleic acid of approximately to purity is obtainable in the openmarket and also l n onnnoncoioom moon onmionooiocm H50 11 The9,11-linoleic acid is converted into the anhydrous sodium salt andreacted mole ior mole with the above intermediate, in presence 01'anhydrous alcohol or some other suitable solvent. This reaction may beindicated thus:

nHnOHCOO i "n 0.11.501 miooooflm.

I CnHuOHC O0 Other alternate procedures may be used, and particularlysome in which the percentage oi mixed glyceride is not as high in theproduct obtained by the described procedure, but still suiilciently highfor the manufacture of valuable products forthe employment of processesherein described. v

In regard to the above esteriilcation procedure or alternate procedure,see the comprehensive article entitled "Polyhydric alcohol esters offatty acids," in Chemical Reviews, volume 8, No. 3, at page 257.

The polymerization of the diene acid is conducted in the same identicalmanner employed for the polymerization of the methyl ester. Thepolymerization of the methyl esteris described in various U. S. patents.as, for example: No. 2,825,040, dated July 27, 1943, to- Cook et al.;2,347,562, dated April 25, 1944, Johnston; 2,857.- 839, dated September12, 1944, Evans et al.

The dimerization of the methyl ester may be indicated in the followingmanner:

2 moles math 1 ester 9,11-octadecadienio acid (ori y present and/orformed by isomerization of 9,12 isomer) (See U. 8. mm No. 2,341,562April 25, 1944, to I bnston, above mentioned.)

In polymerization of polyene acid esters it has been found thattemperatures between about 250 C. and about 350 C. are suitable for thepolymerization. The time required for this polymerization varies notonly with the temperature, but

with the acid. and the particular ester which is used. Generally, aperiod of from about one-half hour to about 50 hours is suitable. and inmost instances, the polymerization may be eflected in not over 12 hours.If a coniugatedunsaturated ester, such as the methyl ester ofoleostearic acid beemployed, a sufllcient degree of polymerization maybe obtained within one-half to one hour at about 300 C.,.whereas, themethyl linolenates and linoleatesgeneraliy require from about 5 to 12hours or more. To speed up the polymeriza- Patent No. 2,207,686, datedJuly 9, 1940, to Schwarcman. In any event. any suitflle procedure isused to prepare the mixed glyceride which has the fol-.-

lowing formula:

cndcmnononcmcn=cn clgmc oocn omen.).cnoncmcn=cnicm)1c0o nomom)icn=on=on=omcnmcoo n 0H=cg oniwnmc omcnmcooon H\H n H 0-0 H. HCHKCHQ; c=c 011970 00011 An examination of the preceding formulaimmediately suggests additional procedures for pro ducing the dimer ofthe mixed glyceride. For instance, a raw material which can be readilyprepared or purchased in the open market, is dirlcinolein. The formulafor such product, ignoring isomeric forms, is, of course:

It becomes obvious that if two moles of diricino- 40 lein could bereacted with one mole of the dimeric acid which has been previouslydepicted in the form of a methyl ester, one would then obtain thedimerized mixed glyceride previously described. The objection to suchprocedure, however, is that reaction cannot be limited to the hydroxylatproximately 250. C., and as a result of a somewhat lower. temperature.-it is sometimes desirable to use a longer time period forisomerization. for instance, a time period as long as twentyfour toforty-eight hours. I

Other means for inducing or hastening or catalyzing polymerization ofthe above described reactants are wellknown. See, for example, U. 8.

tached to the glycerol residue, and, in fact, may involve the ricinoleylhydroxyl radical. Thus, such procedure, although giving fair yields,also gives admixture with other products which preferably are avoided.However, if the methyl ester or ethyl ester of the dimeric acid is usedso esteriflcation involves the elimination of the methyl or I ethylalcohol. then and in that event, the reaction appears to be limitedlargely to involving the glycerol hydroxyl.

Another procedure which immediately suggests 'itself in the formation ofthe monomeric mixed giyceride, is the procedure commonly referred to asre-esteriflcation, cross-esteriflcation, or trans-esterification. Suchprocedure is well known, and in essence,-wou1d involve, for example,mixing two moles of triricinolein with one mole of the total or completeglyceride of 9,11-iinoleic acid dimer. Such migration of the acylradicals takes place at a temperature below the pyrolytic point oftriricinolein, and in presence of an alkaline catalyst. The suitabletemperature is approximately 250 (2., or slightly less, and the timerequired may be comparatively long, for instance, 36 to 72 hours.

In any event, one obtains the dimerized mixed glyceride by any suitableprocedure, and the product employed should preferably contain at least65% or more of the dimerized mixed glycer- 75 ide; some of theprocedures above enumerated access:

will yield -a product markedly in excess of this value. guch mixedglyceride, if carefully prepared, has aviscosity approximately that ofcastor oil. or slightly blow'n'castor oil, a distinctly darker color,and perhaps, a less pleasant odor. The chemical constants, such asmolecular Weight iodine number. hydroxyl number and saponlilcationvalue, approximate the calculated theoretical value. It is tov be notedthat this intermediate is not claimed herein per se.

Such dimerized mixed glyceride previously described-in detail. issubjected to reaction with poly es c' r l? widlv Polybasic carboxy'acids which may be employed in the es terincation reaction may beexemplified by phthalic, succinic, malic, fumaric, citric, citraconic,tricarballylic. maleic, a'dipic. tartaric, oxclip, or thelike'. Theanhydrides, of such polybasic carboxy acids; such as phthalic anhydride,

maleicanhydride, etc., are the equivalents of" the acids, and in somerespects, are even more advantageous than the acids in the productionof-esters. When, reference is made to polybasic cat-boxy acids, theanhydrides thereof are also included; Other suitable polybasic acids maybe prepared by-the diene synthesis which involves condensation ofalpha-beta, unsaturated acids or anhydrides with'compopnds containing aconiugated double bond. For example. the condensation of maleicanhydride' with alpha-terpinene yields a dicarboxy acid which issuitable. Otherpolybasie carbcxy acids may be' prepared similarly by thediene synthesis involving condensation 'of an alpha-beta. unsaturatedmonocarboxy acid with a carboxy acid containing a conjugated doublebond. l'br example, crotonic acid may be condensed with abietic acid,which contains a conjugated double bond, to yield a dicarboxy acidsuitable for use in the manufacture of the herein contemplated products.

It has been found, however, that of all the acids available, thedicarboxy acids having an: carbon atoms or less are particularlypreferable. The choice is to use such acids which are cheap andparticularly resistant to pyrolysis," such as phthalic acid or theanhydride, maleic acid or the anhydride, citraconic acid or theanhydtide, and adipic acid. It is known, of course, that if a dimer ofthe kind aboye described is heated with maleic anhydride or the like, orsome other dienophile, that a more complicated series of reactions willtake place, and this, as a matter of fact, would apply even if thericinoleyl radical were replaced by an oleyl radical. The presentinvention is not concerned with this particular variant. Indeed, maleicacid may even add under appropriate conditions to the double bond whichhas been shown as part of a cyclic structure in a previousrepresentation of the structural for-- mills. ofthejdimerised mixedglyceride.

For convenience then, rather than repeat the above structure, which israther burdensome, it is sufficient to present a simpler form which maybe represented thus:

l Hoacoocn HORCOOCH noacoo n noncoon 6 Such formula shows clearly thatthe dimerized mixed glyceride may serve as a tetrahydric alcohol offairly high molecular weight and that it may be subjected to reaction inthe same way that castor oil, which may be considered a trihydricalcohol, is esteriiled with various polycarboxy acids, particularlyphthalic anhydride, maleic anhydride, citraconic anhydride. and adipicacid. The procedure of reacting castor oil or similar polyhydroxyalcohol esters of hydroxylated fatty acids requires no elaboration.Briefly stated, one pound mole of the dimerized mixed glyceride, forinstance, one pound mole of dimeric 9,11-lincio-diricinolein, is mixedwith a predetermined amount of the selected polycarboxy acid, forinstance, one mole, two moles, three 'moles, or somewhat less than fourmoles. The

- reaction is conducted at any suitable temperature above 175 C. andbelow the pyroly'tic point of either the ricinoleyl radical, or of thepolycarboxylacid selected. Insofar that one can employ any number. ofpolycarboxy acids which are resistant to pyrolysis from a practicalstandpoint, one need only employ a temperature below the pyrolysis ofthe ricinoleyl radical, i. e.. a temperature of approximately 250 0., orslightly less. Such reaction mass is stirred constantly during reaction,and if desired, .a very small quantity of a dried inert gas, such asnitrogen, is passed through during the course of reaction. The objectionto such procedure is only that if the polycarboxy reactant sublimes, asin the case of phthalic anhydride, some may be lost. There is no need toadd the. usual esteriflc'ation catalyst, such as one-tenth to'five-tenths of 1% of toluene sulfonic-acid, but if added, it appears tohasten the reaction. The time of reaction varies, but approximately sixto fifteen hours will serve. Themass should be stirred continuouslyduring reaction. If no inert gas is passed in the mass.

' then any phthalic anhydride or'the like which sublimes, can be scrapedfrom the condenser'by a'continuous scraper and returned to 'the reac-'tion mass. Completeness of the reaction can usually be determined by thefact that the cooled reaction mass stays clear, indicating the absenceof any reactive polycarboxy acid or anhydride.

In any event,'a representative sample can be taken and titrated so as todetermine the acid value, and it is to be noted that at the end of thereaction, the acid value should approximately indicate that one-half ofthe dicarboxy acid car- .boxyls have reacted. The entire process is toproduce a fractional or partial ester having at least one and preferablymore free carboxy'l radicals. As previously-pointed out, a simpledetermination of the acid value denoting the percentage of unreactedcarboxyi radicals in the mechanical mixture at the beginning of thereaction and in the chemical compound at the end of the reaction, willserve. To some degree, it is possible that there is some linkage whereinone mole of the polycarboxy reactant involves two 'moles of the dimer.However, molecular weight determinations on the finished product appearto indicate that there is comparatively a small fraction, if any. of asub-resinous material involving the polyfunctionality of both thedimerized mixed glyceride and the dicarboxy acid. Obviously, thelikelihood for such higher polymer formation increases as the racialratio ofthe polycarboxy'reactant increases, and other factors come intoplay, such as higher temperature of reaction, increased time ofreaction, etc. This conforms to expecta- Mom. v I I acsasse Thepreferred composition represents such compounds as dimeric 9,11 linolodiricinolein mono-acid-phthalate, 9,11-linolo-diricinoleindiacid-phthalate, and similarly, the tri-acidphthalate, and mixtures ofthe tri acidphthalate and the tetra-acid-phthalate. equal interest arethe corresponding acid maleates, corresponding acid adipates. andcorresponding acid citraconates and succinates. Although furtherdescription is unnecessary, it is to be noted that in subsequentexamples some of the preferred products are exemplified by illustrationand structural formulae which are not intended to refer to anyparticular isomer.

Example 1 One pound mole of dimerized 9,11-linolo-diricinolein isreacted with one pound mole of phthalic anhydride.

i H ooion ngoacooon HOROO H HORCOOH HORCOO H For convenience ofdepicting the acid, phthalic acid is shown instead of the anhydride. Thesignificance of R1 has been indicated previously. The procedural stepsare those previously indicated, but briefly, require nothing more orless than reaction for approximately two to six hours, with constantstirring at about 225 C. to 250 C. A catalyst may be added, such asone-fourth of 1% of toluene sulfonic acid, or dried carbon dioxide maybe passed through the mixture, provided safeguards are taken not to losephthalic anhydride by sublimation.

Example 2 Two moles of phthalic anhydride are employed for each mole ofthe dimer. The conditions of reaction are substantially the same aspreviously indicated,

H oogon HIEORCOOCH' noaooo n HORCOOAH ooion nioacoo H Example 3 Themolar proportion of phthalic anhydride is increased so as to introduceapproximately 3% moles of phthalic anhydride per mole of dimer.

Example 4 Adipic acid is used instead of phthalic anhydride in Examples1 to 3, preceding.

Example 5 Succinic acid is used instead of phthalic anhydride inExamples 1 to 3. preceding.

Example 6 Diglycollic acid is used instead of phthalic anhydrideinExamples 1 to 3, preceding.

It is my preference to use heat resistant dicarboxy acids having notover 8 carbon atoms, andparticularly those that are saturated asdistinguished from unsaturated ones, such as maleic acid, or maleicanhydride, citraconic acid or citraconic anhydride. The reason for thislatter preference is simply that as more drastic conditions areemployed, particularly for introduction of higher molal amounts of thedicarboxy acid, maleic acid or the anhydride, or citraconic acid, or theanhydride, may undergo polymerizations by addition or rearrangement, asdistinguished from conditions which normally eliminate water or someother small molecule, provided such reactant employing a carboxyl isused. If, however, the reactions are conducted cautiously so as to avoidany undue complications, one obtains prod ucts of equal value from suchmaterials as maleic anhydride, or citraconic anhydride.

The new chemical products or compounds herein described, are useful forother purposes in addition to demulsification. They may be added, forexample, to metal polishes to give a slight acidity. They may also beemployed as a plasticizer in resin formation, where the acidity of thecarboxyl is not objectionable. I have found that the chemical compoundsherein described, which are particularly desirable for use asdemulsifiers, may also beused as break inducers, in doctor treatment ofthe kind intended to sweeten gasoline. (See U. S. Patent No. 2,157,223,dated May 9, 1939, to Sutton.)

I am aware that valuable products suitable for use as wetting agents,etc., may be prepared by considering the acidic fractional esters hereincontemplated as intermediates. Such intermediates can be subjected tooxyethylation with ethylene oxide, propylene oxide, butyiene oxide,.

glycide and methylglycide, so as to give watersoluble products.Similarly, such intermediates may be reacted with hydroxylated tertiaryamines, particularly triethanolamines, to give acylated derivativeshaving particularly valuable properties for the purposes enumerated inthe present paragraph.

Attention is directed to the fact that the compounds hereincontemplated, although derived essentially from one mole of the dimer,may actually represent sub-resinous materials, in which two or threemoles of the dimer are joined by a polycarboxy acid radical. It becomesobviously dimcult, if not impossible, to present a formula depictingsuch more elaborate and more complicated aspect of the invention.However, in regard to the simpler aspect, that is, derivatives of thedimer, it is to be noted that structural formulae present an adequateportrayal.

As has been previously pointed out, the mixed ester herein contemplatedfor dimerization is referred to as 9,11-1inolo ricin0lein. Thisnomenclature appears to conform with that commonly employed indesignation of mixed glycerides having one linoleyl radical, althoughfrom more formal nomenclature, itis possible that the expression9,11-linoleyl-diricinolein would be appropriate, since in essence ahydrogen atom of diricinolein has been replaced by the 9,11-linoleylradical.

Having thus described my invention, what I claim as new and desire tosecure by Letters Patent is:

1. An acidic partial ester of a polycarboxy acid v with dimerized9,11-linol-diricinolein.

2. An acidic partial ester of a dicarboxy acid with dimerized9,11-linolo-diricinolein.

3. An acidic partial ester of a dicarboxy acid having less than 9 carbonatoms with dimerized 9,11-linolo-diricinoiein.

4. An ester having at least one ricinoleyl hydroxyl hydrogen atom ofCH(CH2)1COOHH replaced by the radical OCR2COOH of the dicarboxy acidHQOCRzCOOI-I in which R: is an organic radical having less than '7carbon atoms linked to the COOH groups through different carbon atoms.

5. An ester having more than one ricinoleyl hydroxyl hydrogen atom ofcH. cmncnoncmcn=cmcim1c00 5B 5 cH, omncnonomcn=cn cm 1co0 H CH=CH CH 0 cs( H|)|H\g g/CHI(CH:)1COOHH H H ormcnm =C(CH;)1COO H omwrmlcnoncncn=cmcrm1c0o 11 CHI(CH:)5CHOHCHICH=OHKJH2 1COOEH 5 replaced 'by theradical -OCR:CO0H of the dicarboxy acid H0.0CR/2COOH in which R: is anorganic radical having less than 7 carbon atoms linked to the COOHgroups through different carbon atoms. 2o 6. The acidic fractional esterof claim 5, wherein HO.OCR2COOH is phthalic acid.

7. The acidic fractional ester of claim 5, wherein H0.0CR:COOH is adipicacid.

8. The acidic fractional ester of claim 5,wherein HO.OCR2COOH isdiglycollic acid.

MELVDI DE GROO'I'E.

amancas crrab The following references are of record in the file of thispatent:

UNITED STATES PATENTS Number Name Date 2,027,467 Brubaker Jan. 14, 19362,310,395 Carruthers Feb. 9, 1943 2.416.485 Lasher Feb. 25. 1947

